US8128980B2 - Method for production of water-soluble polysaccharide - Google Patents

Method for production of water-soluble polysaccharide Download PDF

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US8128980B2
US8128980B2 US12/451,900 US45190008A US8128980B2 US 8128980 B2 US8128980 B2 US 8128980B2 US 45190008 A US45190008 A US 45190008A US 8128980 B2 US8128980 B2 US 8128980B2
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water
polysaccharide
soluble
protein
soluble soybean
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US20100136204A1 (en
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Nanae Fujii
Junko Tobe
Akihiro Nakamura
Ryuji Yoshida
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Fuji Oil Co Ltd
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Fuji Oil Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0045—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Galacturonans, e.g. methyl ester of (alpha-1,4)-linked D-galacturonic acid units, i.e. pectin, or hydrolysis product of methyl ester of alpha-1,4-linked D-galacturonic acid units, i.e. pectinic acid; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C11/00—Milk substitutes, e.g. coffee whitener compositions
    • A23C11/02—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins
    • A23C11/10—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins containing or not lactose but no other milk components as source of fats, carbohydrates or proteins
    • A23C11/103—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins containing or not lactose but no other milk components as source of fats, carbohydrates or proteins containing only proteins from pulses, oilseeds or nuts, e.g. nut milk
    • A23C11/106—Addition of, or treatment with, microorganisms
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00—Milk preparations; Milk powder or milk powder preparations
    • A23C9/12—Fermented milk preparations; Treatment using microorganisms or enzymes
    • A23C9/13—Fermented milk preparations; Treatment using microorganisms or enzymes using additives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00—Milk preparations; Milk powder or milk powder preparations
    • A23C9/152—Milk preparations; Milk powder or milk powder preparations containing additives
    • A23C9/154—Milk preparations; Milk powder or milk powder preparations containing additives containing thickening substances, eggs or cereal preparations; Milk gels
    • A23C9/1542—Acidified milk products containing thickening agents or acidified milk gels, e.g. acidified by fruit juices
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L11/00—Pulses, i.e. fruits of leguminous plants, for production of food; Products from legumes; Preparation or treatment thereof
    • A23L11/60—Drinks from legumes, e.g. lupine drinks
    • A23L11/65—Soy drinks
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52—Adding ingredients
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52—Adding ingredients
    • A23L2/66—Proteins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/17—Amino acids, peptides or proteins
    • A23L33/185—Vegetable proteins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2250/00—Food ingredients
    • A23V2250/50—Polysaccharides, gums
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/06—Pectin; Derivatives thereof

Definitions

  • the present invention relates to a method for producing a novel water-soluble soybean polysaccharide which enables to stabilize a protein that has not been sufficiently stabilized with the conventional water-soluble soybean polysaccharide, in a pH range around the isoelectric point of the protein, and also relates to a novel dispersion stabilizer for a protein, containing the produced polysaccharide as an active ingredient.
  • Patent Document 1 describes that a water-soluble soybean polysaccharide is obtained by degrading water-insoluble vegetable fibers containing a protein under acidic conditions around the isoelectric point of the protein at a high temperature.
  • pectin and carboxymethylcellulose other than water-soluble soybean polysaccharides have been used as a dispersion stabilizer for a protein under acidic conditions.
  • a milk protein can be dispersed and stabilized in a pH range around the isoelectric point of a milk protein, i.e. in a pH range of about 4.2 to 4.8, which is a pH range such that stabilization with the water-soluble soybean polysaccharides is difficult, but the beverage produced have viscous or pasty mouth feel. It is difficult to obtain a beverage having a low viscosity in a pH range around the isoelectric point of the milk protein.
  • a milk protein has a positive charge under acidic conditions at or below the isoelectric point.
  • Polysaccharides particularly pectin and a water-soluble soybean polysaccharide.
  • Non-Patent Document 1 It is thought that aggregation and precipitation of proteins are suppressed due to electric repulsion and steric hindrance by ionic and hydrophobic bonding to the protein surface via own negative charges of polysaccharides which distribute to dispersion stability of a milk protein.
  • a lot of approaches to increasing the negative charges of the polysaccharides have been made so far.
  • carboxymethylcellulose as mentioned above is increased negative charges by introducing carboxymethyl group into cellulose.
  • a stabilizer which enables to stabilize the dispersion of a milk protein at a low viscosity in a pH range around the isoelectric point of the milk protein has not been obtained yet.
  • investigation focused on the molecular mass of stabilizers has not been known so far.
  • An object of the present invention is to provide a novel water-soluble soybean polysaccharide which is produced by imparting a function of stabilizing a protein in a pH range around the isoelectric point of the protein to a water-soluble soybean polysaccharide.
  • Another object of the present invention is to provide a novel dispersion stabilizer which enables to stabilize the dispersion of a protein in a pH range around the isoelectric point of the protein, and acidic protein food and beverage using the dispersion stabilizer.
  • a molecular mass of a polysaccharide to be added contributes much to dispersion stability of a protein in a pH range around the isoelectric point.
  • the present invention has been completed based on the finding that a water-soluble polysaccharide which has been obtained by crosslinking water-soluble soybean polysaccharide can stabilize a protein in a pH range around the isoelectric point of the milk protein, while such stabilization could not be attained by the conventional water-soluble soybean polysaccharides.
  • the present invention is:
  • a method for producing a water-soluble polysaccharide which comprises carrying out a crosslinking treatment of a water-soluble soybean polysaccharide.
  • a dispersion stabilizer for a protein comprising a crosslinked water-soluble soybean polysaccharide as an active ingredient.
  • An acidic protein food or beverage comprising the dispersion stabilizer according to (4).
  • a novel water-soluble soybean polysaccharide having a high molecular mass different from the conventional can be obtained, and novel acidic protein beverage and food can be provided by using the water-soluble soybean polysaccharide which enables to stabilize the dispersion of a protein which has not hitherto been able to be stabilized, in a pH range of the isoelectric point of the protein.
  • the water-soluble soybean polysaccharide used in the present invention includes water-soluble soybean polysaccharides obtained by various methods, and, for example, water-soluble soybean polysaccharides as described in Patent Document 1 can be used.
  • a water-soluble soybean polysaccharide can be obtained by extracting a raw material such as defatted soybean cake (soymeal) and okara which is by-product in the production of tofu, soy milk or soy protein isolate, under aqueous conditions at a high temperature under a weakly acidic conditions of the isoelectric point of the protein, and subjecting the extract to solid-liquid separation.
  • the water-soluble soybean polysaccharide obtained in this manner may be subjected to crosslinking reaction of the extraction filtrate or purified extraction filtrate, or may be subjected to crosslinking reaction of a further dried product from the extraction filtrate or its purified product.
  • the crosslinking treatment enables to directly form an intramolecular or intermolecular crosslinkage of water-soluble soybean polysaccharides, or may construct a crosslinkage via a crosslinking agent.
  • a direct intermolecular crosslinking method for polysaccharides it is carried out by adding an aqueous solution of various acids including a mineral acid such as hydrochloric acid to a water-soluble soybean polysaccharide at a rate of 2 to 50 mmol per 100 g of the polysaccharide, adjusting the water content to 0.5 to 20%, and then heating the mixture at 100° C. to 160° C.
  • a crosslinking reaction may be carried out by treating a water-soluble soybean polysaccharide with an enzyme or a radiation.
  • a method for crosslinking a water-soluble polysaccharide via a crosslinking agent is concretely exemplified.
  • a variety of crosslinking agents are added to an aqueous solution of a water-soluble soybean polysaccharide.
  • the crosslinking agent herein mentioned includes, but not particularly limited to, phosphoric acid compounds (e.g. phosphoric acid, phytic acid, polyphosphoric acid, metaphosphoric acid, phosphoric anhydride, hexametaphosphoric acid, trimetaphosphoric acid, etc.) and salts thereof, phosphorus oxychloride, epichlorohydrin, formaldehyde, glutaraldehyde, diepoxyalkane and diepoxyalkene, and the like.
  • phosphoric acid compounds e.g. phosphoric acid, phytic acid, polyphosphoric acid, metaphosphoric acid, phosphoric anhydride, hexametaphosphoric acid, trimetaphosphoric acid, etc.
  • trimetaphosphoric acid or its salt is preferable in view of the reaction efficiency, and especially, trimetaphosphoric acid or its salt is most preferable.
  • the amount of the crosslinking agent to be added differs depending on the kind of the crosslinking agents and the concentration of the water-soluble soybean polysaccharides, but in the case where trimetaphosphoric acid is used for a 5% by weight aqueous solution of a water-soluble soybean polysaccharide, the amount of trimetaphosphoric acid is preferably 1% by weight or more to 100% by weight or less, more preferably 10% by weight or more to 80% by weight or less, and most preferably 20% by weight or more to 50% by weight or less.
  • the amount of the crosslinking agent is too little, the efficiency of the crosslinking formation becomes low, and if the amount of the crosslinking agent is too large, viscosity of the solution suddenly increases, and gelation occurs sometimes during the treatment. It is necessary to adjust the concentration of the crosslinking agent to be added according to the concentration of the water-soluble soybean polysaccharide in a reaction solution, and when the concentration of the water-soluble soybean polysaccharide is high, the amount of the crosslinking agent to be added can be less than the above-described value.
  • salts can be added so as to adjust the viscosity of the soybean polysaccharide at the time of the reaction.
  • Such salts are soluble in water and preferred examples thereof include sodium chloride, calcium chloride, sodium sulphate, and sodium carbonate.
  • the alkali condition is preferably pH 10 or more, more preferably pH 12 or more, and preferably less than pH 14, more preferably less than pH 13.
  • the heating condition is preferably 40° C. or higher, more preferably 50° C. or higher, most preferably 55° C. or higher, and preferably 90° C. or lower, more preferably 80° C. or lower.
  • the heating time is preferably 10 minutes or longer, more preferably 30 minutes or longer, and preferably not more than 4 hours, more preferably not more than 2 hours.
  • the heating pH and heating temperature are high, the water-soluble soybean polysaccharide is sometimes degraded by ⁇ -elimination, and when the heating pH and heating temperature are low, crosslinking reactivity is poor.
  • crosslinkage formation takes place in the water-soluble soybean polysaccharides, thereby producing a high molecular fraction and enabling to enhance an ability to stabilize the dispersion of a protein.
  • the water-soluble soybean polysaccharides obtained by using a phosphoric acid compound or its salt as a crosslinking agent contains a phosphoric acid diester bond in the molecule and is a water-soluble soybean polysaccharide which is polymerized by phosphoric acid diester bonds, as confirmed in Example 3 described later.
  • the polymer material includes, but not particularly limited to, polysaccharides (e.g.
  • starch modified starch, dextrin, cellulose, microcrystalline cellulose, fermented cellulose, various modified celluloses, agar, carrageenan, furcellaran, guar gum, locust bean gum, tamarind seed polysaccharides, tara gum, gum arabic, tragacanth gum, karaya gum, pectin, xanthan gum, pullulan, gellan gum, etc.), proteins (e.g. milk protein, soybean protein, etc.), and fractions thereof. Two or more of the polymer materials can be mixed together.
  • the water-soluble soybean polysaccharide is not a main component in the crosslinked compound, it is desirable that the water-soluble soybean polysaccharide is incorporated in an amount of not less than the half of the crosslinked compound so as to achieve a stronger effect.
  • crosslinkage formation between the water-soluble soybean polysaccharide and other polymer material such formation is carried out in a similar manner to the case using the water-soluble soybean polysaccharide alone, and it is also possible to make crosslinkages directly or via other crosslinking agent. Moreover, the reaction method and the conditions in that case are according to the case of the water-soluble soybean polysaccharide alone.
  • the resulting water-soluble soybean polysaccharide Although it is possible to use the resulting water-soluble soybean polysaccharide as it is, purification is desirable so as to fulfill its function.
  • purification is desirable so as to fulfill its function.
  • an extracted water-soluble soybean polysaccharide is crosslinked as it is, it is preferable to remove proteins contaminated in the water-soluble soybean polysaccharide because they give an adverse effect on the water-soluble soybean polysaccharide for dispersion stability of a protein.
  • the method for removal of the proteins includes a method where proteins are aggregated after pH adjustment and removed by a separation means such as pressure filtration-separation, centrifugation, filtration, and membrane separation; a method where proteins are degraded with an arbitrary protease; and a purification method where impurities are removed by adsorption using an activated carbon or a resin.
  • a separation means such as pressure filtration-separation, centrifugation, filtration, and membrane separation
  • a method where proteins are degraded with an arbitrary protease and a purification method where impurities are removed by adsorption using an activated carbon or a resin.
  • the pH is adjusted to around the isoelectric point of soybean protein, i.e. about pH 4.5, preferably pH 3.5 to 5.0, and the precipitated proteins are separated and removed.
  • acids used for pH adjustment and any acids can be utilized, including inorganic acids (e.g.
  • hydrochloric acid sulfuric acid, phosphoric acid, etc.
  • organic acids e.g. acetic acid, citric acid, lactic acid, etc. It is preferable to use one of these acids or combine two or more kinds of these acids for removing the proteins.
  • Any desalting purification methods can be used so long as they can separate and remove salts.
  • Such purification method includes a precipitation method using a polar organic solvent (e.g. methanol, ethanol, isopropanol, acetone, etc.); an electrodialysis treatment; an ion-exchange resin or hydrophobic resin treatment; and a membrane fractionation using a UF membrane. Single method or combination use of two or more of these methods is preferred.
  • a powdered water-soluble soybean polysaccharide can be obtained by sterilizing a solution of thus purified water-soluble soybean polysaccharide through plate sterilization or steam sterilization, and then pulverizing after freeze-drying, spray-drying, heat-drying, or the like.
  • the water-soluble soybean polysaccharide obtained by the above-described method has contained a polysaccharide component with a molecular mass of 0.5 million to 10 million when analyzed by gel filtration HPLC (TSKgel-G-5000 PWXL; TOSOH 7.8 mm ⁇ 30 cm).
  • the molecular mass of the water-soluble soybean polysaccharide has been a value measured using a standard reference pullulan P-82 (Showa Denko K.K.).
  • analysis conditions have been as follows: mobile phase, 50 mM sodium acetate solution (pH 5.0); flow rate, 1.0 ml/min; sugar has been detected with an RI detector.
  • a total peak area has been equivalent to the total mass of the polysaccharide, and the ratio of the peak area of the polysaccharide ingredient with a molecular mass of 0.5 million to 10 million to the total peak area has been calculated as a content rate of the high molecular fraction.
  • Dispersion stability of the protein becomes effective when the content rate of the high molecular fraction of the water-soluble soybean polysaccharide obtained is 5% or more, preferably 20% or more, and more preferably 30% or more.
  • the content rate of the high molecular fraction in the water-soluble soybean polysaccharide not exceeding 95% is preferable because the limitation of use by the viscosity etc. is few.
  • the present invention relates to a protein dispersion stabilizer which can prevent the aggregation of protein particles in an aqueous solution, and can retain a stable dispersion state.
  • the function thereof is effective in range of pH 4.2 to 5.2, preferably pH 4.4 to 4.8, and more preferably pH 4.4 to 4.6, and is suitable for acidic protein food and beverage, particularly for acidic protein beverage.
  • Dispersion of a milk protein in range of pH less than 4.2 can be attained with a conventional water-soluble soybean polysaccharide.
  • the milk protein starts to dissolve in range of pH more than 5.2, therefore, it is not necessary to use a dispersing agent.
  • acidic protein food and beverage can be prepared in range of pH 4.2 to 5.2.
  • the dispersion stabilizer of the present invention is easy to generate acidity and its flavor is good, therefore, it can be utilized for wide applications. Moreover, there is also a feature of low viscosity in the stabilizer.
  • various gums and proteins, and degraded products thereof can be used in combination, if necessary. Examples of the substances for combination use include, for example, polysaccharides (e.g.
  • starch modified starch, various celluloses, agar, carrageenan, furcellaran, guar gum, locust bean gum, tamarind seed polysaccharides, tara gum, gum arabic, tragacanth gum, karaya gum, pectin, xanthan gum, pullulan, gellan gum, etc.) as well as proteins (e.g. gelatin, etc.).
  • the acidic protein food and beverage of the present invention are acidic protein food and beverage containing animal and vegetable proteins, regardless of whether the food and beverage are solid or liquid form.
  • animal proteins refer to mainly animal milk such as cow milk and goat milk, and specific examples include cow milk, skim milk, whole milk powder, skim milk powder, whey powder, sweetened milk, condensed milk, concentrated milk, processed milk fortified with minerals (e.g. calcium, etc.) or vitamins, and fermented milk.
  • the vegetable proteins include soybean milk obtained mainly from soybeans, and specific examples include soybean milk, defatted soybean milk, soybean milk powder, defatted soybean milk powder, soybean protein isolate, and fermented products thereof.
  • the acidic protein beverage among the acidic protein food and beverage is protein beverage obtained by fermenting a beverage using animal milk, soybean milk or the like, or by adding fruit juices or organic acids (e.g. citric acid, lactic acid, etc.) or inorganic acids (e.g. phosphoric acid) to the beverage, to make the pH range acidic.
  • organic acids e.g. citric acid, lactic acid, etc.
  • inorganic acids e.g. phosphoric acid
  • the acidic protein food among the acidic protein food and beverage includes acidic frozen dessert such as acidic ice cream and frozen yogurt obtained by adding organic acids or fruit juices to frozen dessert containing milk components such as ice cream; acidic dessert obtained by adding organic acids or fruit juices, etc. to gelled food such as pudding and bavarois; coffee beverage; acidic cream; yogurt and the like; using the above animal milk or soy milk as a raw material.
  • the water-soluble soybean polysaccharide produced by the present invention fulfills a function of stabilizing a dispersion of a protein, particularly in the acidic protein beverage.
  • the water-soluble soybean polysaccharide of the present invention can stabilize the dispersion of, a protein in a pH range around the isoelectric point of the protein in which the conventional water-soluble soybean polysaccharide cannot stabilize.
  • effects can be observed in any proteins, but milk protein or soybean protein is preferable, and milk protein is the most general-purpose acidic food and beverage which shows an excellent effect of the dispersion stabilizer of the present invention and is most preferable.
  • an acidic protein beverage with a viscosity of 10 mPa ⁇ s or less can be prepared by using the dispersion stabilizer of the present invention in a mixing ratio of, for example, Table 1 as shown later.
  • a lactic acid bacterium could not live.
  • food and beverage having a pH range at which a lactic acid bacterium can be alive can be made.
  • a lactic acid bacterium beverage of non-heating and living bacterium can be prepared using lactic acid bacterium-fermented milk.
  • the protein dispersion stabilizer of the present invention is particularly effective for acidic food and beverage having a protein concentration of 10% by weight or less, and good protein dispersion stability is shown around a pH range in the vicinity of the isoelectric point of the protein by adding 0.05 to 2.0% by weight, more preferably 0.1 to 1.5% by weight, and further preferably 0.2 to 1.0% by weight of such stabilizer to the acidic food and beverage.
  • protein food and beverage having a pH of about 4.2 to 5.2 can be prepared, and it can prevent from aggregation particularly at a pH of 4.4 to 4.6. If the concentration of the dispersion stabilizer is high, there is a case to affect a flavor of food and beverage, and if the concentration of the dispersion stabilizer is low, there is a case being not able to fulfill an ability of dispersion stabilization.
  • a 5% aqueous solution of water-soluble soybean polysaccharide (SOYAFIVE S-DA100: manufactured by Fuji Oil Co., Ltd.) was prepared and heated in a boiling water bath for 5 minutes.
  • Sodium trimetaphosphate was dissolved in the aqueous polysaccharide solution so as to have a final concentration of 2% and the resulting solution was adjusted to pH 12 with an aqueous sodium hydroxide solution.
  • the reaction solution was allowed to react with stirring at 60° C. for one hour.
  • the insolubles produced were removed by centrifugation (8,000 rpm, 30 minutes) to obtain a supernatant as polysaccharides.
  • the polysaccharide solution was precipitated with ethanol having a final concentration of 60% by weight, and purified with an aqueous ethanol solution of 90% by weight to give the precipitates, which were then air-dried to obtain a water-soluble soybean polysaccharide A.
  • Water-soluble soybean polysaccharides B, C, D, E, F, and G were obtained in a similar manner to the production procedure of water-soluble soybean polysaccharide A except that the pH was adjusted to 8, 9, 10, 11, 13, and 14, respectively, after addition of sodium trimetaphosphate in the production of water-soluble soybean polysaccharide A.
  • Water-soluble soybean polysaccharides H, I, J, K, and L were obtained in a similar manner to the production procedure of water-soluble soybean polysaccharide A except that the reaction temperature was set to 40° C., 50° C., 70° C., 80° C., and 90° C., respectively, in the production of water-soluble soybean polysaccharide A.
  • a 2.5% aqueous solution of water-soluble soybean polysaccharide (SOYAFIVE S-DA100) was prepared and dextrin (PINEDEX #100, manufactured by Matsutani Chemical Industry Co., Ltd.) was dissolved in the solution to a concentration of 2.5%.
  • dextrin PINEDEX #100, manufactured by Matsutani Chemical Industry Co., Ltd.
  • Trimetaphosphoric acid was dissolved in the aqueous polysaccharide solution so as to have a final concentration of 2% and the resulting solution was adjusted to pH 12 with an aqueous sodium hydroxide solution.
  • the reaction solution was allowed to react with stirring at 60° C. for one hour.
  • the insolubles produced were removed by centrifugation (8,000 rpm, 30 minutes) to obtain a supernatant as polysaccharides.
  • the polysaccharide solution was precipitated with an aqueous ethanol solution having a concentration of 60% by weight, and purified with an aqueous ethanol solution of 90% by weight to give the precipitates, which were then air-dried to obtain a water-soluble soybean polysaccharide M.
  • a 2.5% aqueous solution of water-soluble soybean polysaccharide (SOYAFIVE S-DA100) was prepared and HM pectin (USP-H: manufactured by Sansho Co., Ltd.) was dissolved in the solution to a concentration of 2.5%.
  • the resulting solution was heated in a boiling water bath for 5 minutes.
  • Trimetaphosphoric acid was dissolved in the aqueous polysaccharide solution so as to have a final concentration of 2% and the solution was adjusted to pH 12 with an aqueous sodium hydroxide solution.
  • the reaction solution was allowed to react with stirring at 60° C. for one hour.
  • the insolubles produced were removed by centrifugation (8,000 rpm, 30 minutes) to obtain a supernatant as polysaccharides.
  • the polysaccharide solution was precipitated with an aqueous ethanol solution having a concentration of 60% by weight, and purified with an aqueous ethanol solution of 90% by weight to give the precipitates, which were then air-dried to obtain a water-soluble soybean polysaccharide N.
  • the polysaccharide solution was precipitated with an aqueous ethanol solution of 60% by weight, and purified with an aqueous ethanol solution of 90% by weight to give the precipitates, which were then air-dried to obtain a water-soluble soybean polysaccharide O.
  • the molecular mass of water-soluble soybean polysaccharides was determined according to the above-described gel filtration HPLC for measurement of molecular mass distribution.
  • Water-soluble soybean polysaccharide A and water-soluble soybean polysaccharide are shown in FIG. 1 . From this Figure, it was able to confirm that the water-soluble soybean polysaccharide was polymerized by crosslinking. With respect to quantification of the high molecular fraction, it was assumed that a total peak area was equivalent to the total mass of the polysaccharide, and the ratio of the peak area of the polysaccharide component with a molecular mass of 0.5 million to 10 million to the total peak area was quantified.
  • aqueous solution containing 21% by weight of skim milk powder (manufactured by Yotsuba Co., Ltd.) was prepared and sterilized under heating at 95° C. with stirring. After cooling, commercially available plain yogurt was inoculated thereto and fermented in a constant temperature oven of 40° C. until the pH became 4.6. The fermented yogurt was homogenized with a homogenizer (150 kgf) by crushing the curd.
  • Each aqueous solution of the water-soluble soybean polysaccharides A to O produced in each Production Example and Comparative Production Example, water, granulated sugar solution and fermented milk were mixed together in an ice-water bath in a mixing ratio as shown in Table 1, and the mixture was adjusted to an arbitrary pH with a 50 wt %-solution of citric acid on ice.
  • the mixed solution was homogenized with a homogenizer (150 kgf).
  • the solution was transferred to a glass bottle, sealed up, and sterilized under heating in a warm water bath of 80° C. for 20 minutes.
  • Viscosity One week after the preparation, viscosity was measured with a BM-type viscometer (rotor No. 1, 60 rpm, 1 min).
  • the precipitation rate was expressed in terms of the following criteria:
  • Supernatant The presence or absence of aggregation after heat sterilization of the supernatant, and the presence or absence of the supernatant on the upper surface of the solution was judged visually. The symbol “+” indicated that there was a supernatant and the symbol “ ⁇ ” indicated that there was no supernatant.
  • Stability of the acidic milk beverages was improved with the water-soluble polysaccharides which had been crosslinked with dextrin, starch, or pectin, respectively, i.e. both of water-soluble polysaccharides M and N.
  • the water-soluble soybean polysaccharide O which had been treated by simultaneous deesterification showed a very high stability to the beverages.
  • Water-soluble soybean polysaccharide A was degraded with Pectinex Ultra SP-L (manufactured by Novozymes A/S Co.) and served as a sample for mass spectrometry.
  • MALDI-TOF-MS analysis and MS/MS analysis were carried out on the water-soluble soybean polysaccharide degraded by the enzyme ( FIGS. 2 and 3 ).
  • a mass peak of 365 derived from the bonding of a phosphoric acid residue and two molecules of arabinose was confirmed by MALDI-TOF-MS analysis ( FIG. 2 ).
  • an MS/MS analysis was further carried out. Since the peak derived from the arabinose was not observed ( FIG. 3 ) though the glycoside bond is broken by MS/MS analysis due to its comparatively weak bonding force, it was thought that there was no structure wherein a phosphoric acid residue was linked to the end of the glycoside bond formed from two arabinose molecules, but there was only a structure wherein the phosphoric acid residue was positioned at the central site and the arabinose was linked at the both ends.
  • the mass peak of 365 was considered to be derived from a structure that the phosphoric acid residue was positioned at the central site and arabinose residues were linked to the both ends, and it was supposed that the water-soluble soybean polysaccharide A had a phosphoric acid diester structure wherein sugar chains were crosslinked via the phosphoric acid residues.
  • the homogenized solution was filled into a cup container, immersed in cold water to form a jelly, which was stored in a refrigerator for one week.
  • the resulting jelly was a jelly being free from protein aggregation and syneresis phenomenon at the stage during treatment and after storage, and having a refreshing acidity.
  • FIG. 1 is a chromatogram of HPLC gel filtration of water-soluble soybean polysaccharide A and water-soluble soybean polysaccharide (SOYAFIVE S-DA100).
  • FIG. 2 is a chart where a water-soluble soybean polysaccharide which has been degraded with an enzyme is analyzed by MALDI-TOF-MS.
  • FIG. 3 is a chart where the sample of FIG. 2 is further analyzed by MS/MS.

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JP5510334B2 (ja) * 2008-11-06 2014-06-04 不二製油株式会社 洗浄剤組成物
WO2010061570A1 (ja) * 2008-11-27 2010-06-03 不二製油株式会社 微粒子物質の分散方法
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MX340232B (es) * 2010-01-22 2016-07-01 Unilever N V * Uso prebiotico de polisacarido de soja soluble en agua.
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CN102793019A (zh) * 2011-05-25 2012-11-28 周鑫 一种奶酪复合物
FR2976945B1 (fr) 2011-06-24 2017-12-29 Fuji Oil Co Ltd Polysaccharide pectique et procede de production de celui-ci
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6140302A (ja) 1984-07-31 1986-02-26 Nichiden Kagaku Kk 架橋多糖類
JPH03280768A (ja) 1990-03-29 1991-12-11 Nec Corp Ｉｃカード電話方式
JPH05230101A (ja) 1992-02-24 1993-09-07 Fuji Oil Co Ltd 水溶性多糖類の水不溶化法
JPH06256402A (ja) 1993-03-03 1994-09-13 Japan Tobacco Inc 水溶性多糖の製造方法
US5587197A (en) 1990-02-07 1996-12-24 Fuji Oil Company, Ltd. Process for production of water-soluble vegetable fiber
JP2599477B2 (ja) 1990-02-09 1997-04-09 不二製油株式会社 水溶性植物繊維の製造方法
JPH11240902A (ja) 1998-02-25 1999-09-07 Fuji Oil Co Ltd 水溶性ヘミセルロースの製造法
US5968794A (en) * 1991-06-04 1999-10-19 Biovector Therapeutics S.A. Biodegradable particulate vector for transporting molecules having biological activity
US6004616A (en) 1990-02-07 1999-12-21 Fuji Oil Company, Ltd. Biodegradable vegetable film
JP2000279104A (ja) 1999-01-26 2000-10-10 Sanei Gen Ffi Inc 良好な物性を有する製剤組成物
JP3280768B2 (ja) 1993-08-20 2002-05-13 三栄源エフ・エフ・アイ株式会社 酸性乳飲料の製造方法
US7229658B1 (en) 1998-10-28 2007-06-12 San-Ei Gen F.F.I., Inc Compositions containing sucralose and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100863870B1 (ko) * 2004-06-21 2008-10-15 에보닉 스톡하우젠 게엠베하 수분 흡수성 다당류 및 이의 제조방법
DE102004030182A1 (de) * 2004-06-22 2006-01-12 Stockhausen Gmbh Wasserabsorbierendes Polysaccharid sowie ein Verfahren zu seiner Herstellung
KR100688075B1 (ko) * 2005-06-08 2007-03-02 주식회사 신동방씨피 수용성 대두 올리고당류 분말의 제조방법
CN1970578B (zh) * 2006-11-30 2010-05-12 华南理工大学 豆渣中水溶性大豆多糖的微波提取方法

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6140302A (ja) 1984-07-31 1986-02-26 Nichiden Kagaku Kk 架橋多糖類
US5587197A (en) 1990-02-07 1996-12-24 Fuji Oil Company, Ltd. Process for production of water-soluble vegetable fiber
US6004616A (en) 1990-02-07 1999-12-21 Fuji Oil Company, Ltd. Biodegradable vegetable film
US6569473B2 (en) 1990-02-07 2003-05-27 Fuji Oil Company, Limited Process for production of water-soluble vegetable fibers, biodegradable film, paste, chewing gum and low calorie food products
US6280526B1 (en) 1990-02-07 2001-08-28 Fuji Oil Company, Limited Process for production of water-soluble vegetable fibers, biodegradable film, paste, chewing gum and low calorie food products
JP2599477B2 (ja) 1990-02-09 1997-04-09 不二製油株式会社 水溶性植物繊維の製造方法
JPH03280768A (ja) 1990-03-29 1991-12-11 Nec Corp Ｉｃカード電話方式
US5968794A (en) * 1991-06-04 1999-10-19 Biovector Therapeutics S.A. Biodegradable particulate vector for transporting molecules having biological activity
JPH05230101A (ja) 1992-02-24 1993-09-07 Fuji Oil Co Ltd 水溶性多糖類の水不溶化法
JPH06256402A (ja) 1993-03-03 1994-09-13 Japan Tobacco Inc 水溶性多糖の製造方法
JP3280768B2 (ja) 1993-08-20 2002-05-13 三栄源エフ・エフ・アイ株式会社 酸性乳飲料の製造方法
JPH11240902A (ja) 1998-02-25 1999-09-07 Fuji Oil Co Ltd 水溶性ヘミセルロースの製造法
US7229658B1 (en) 1998-10-28 2007-06-12 San-Ei Gen F.F.I., Inc Compositions containing sucralose and application thereof
JP2000279104A (ja) 1999-01-26 2000-10-10 Sanei Gen Ffi Inc 良好な物性を有する製剤組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
International Search Report issued Jul. 15, 2008 in International (PCT) Application No. PCT/JP2008/059773.
J. Liu et al., "Addition of Pectin and Soy Soluble Polysaccharide Affects the Particle Size Distribution of Casein Suspensions Prepared from Acidified Skim Milk", J. Agric. Food Chem., vol. 54, No. 17, pp. 6241-6246, 2006.

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